CN1167655C - Process for production of perfluoroalkadienes - Google Patents
Process for production of perfluoroalkadienes Download PDFInfo
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- CN1167655C CN1167655C CNB008182779A CN00818277A CN1167655C CN 1167655 C CN1167655 C CN 1167655C CN B008182779 A CNB008182779 A CN B008182779A CN 00818277 A CN00818277 A CN 00818277A CN 1167655 C CN1167655 C CN 1167655C
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- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
A process for producing perfluoroalkadiene compounds of the general formula (I): CF2=CF-(CF2)n-4-CF=CF2 (wherein n is an integer of 4 to 20) by deiodofluorination of compounds of the general formula (II): I-(CF2)n-I (wherein n is as defined above), characterized in that the deiodofluorination is conducted in the presence of metallic zinc and a nitrogen-containing organic compound.
Description
Technical field
The present invention relates to have the preparation method of the perfluor alkadiene of terminal double link.
Background technology
Perfluorobutadiene can be used as dry corrosion gas (Chemical Week, October13 (1999), 47 pages), is used to make the monomer (the not Japanese patent gazette 26240/1987 and 141935/1988 of Shening) of viton etc.
In the Japanese patent gazette of not examining 26240/1987 and 141935/1988, disclose in the presence of the neutral hydrocarbon solvent, under-80 ℃～+ 150 ℃ temperature, use the organometallic compound of Mg, Zn, Cd or Li, the method for the perfluor alkadiene that takes off IF prepared in reaction formula (I) expression of the compound of through type (II) expression.
CF
2＝CF-(CF
2)
n-4-CF＝CF
2 (I)
(in the formula, n is 4～20 integer)
I-(CF
2)
n-I (II)
(in the formula, the definition of n is the same)
But the defective of these organometallic compounds (n-Butyl Lithium, ethylmagnesium bromide etc.) is expensive and is difficult to handle, and is easy to decompose.
Disclosure of an invention
An object of the present invention is to provide and do not use expensive and reluctant reagent, easily prepare the method for perfluor alkadiene.
The present inventor studies the method for the perfluor alkadiene compound that takes off IF prepared in reaction formula (I) of the compound of through type (II) expression, the result is surprised to find that, replace organometallic compound such as n-Butyl Lithium to contact with the compound that formula (II) is represented with nitrogenous organic compound by metallic zinc, can highly selective and obtain target compound (I) with high yield.
The present invention relates to following 1-4 item:
The 1st. the method for the perfluor alkadiene compound that takes off IF prepared in reaction formula (I) expression of the compound of a kind of through type (II) expression,
CF
2＝CF-(CF
2)
n-4-CF＝CF
2 (I)
(in the formula, n is 4～20 integer)
I-(CF
2)
n-I (II)
(in the formula, the definition of n is the same)
The method is characterized in that, in the presence of metallic zinc and organic compounds containing nitrogen, take off the IF reaction.
The 2nd. the method for the 1st record, wherein nitrogenous organic compound is to be selected from N, dinethylformamide, N,N-dimethylacetamide, N, N-diisopropyl formamide, triethylamine, pyridine, picoline, N-N-methyl-2-2-pyrrolidone N-, quinoline and toluquinoline at least a.
The 3rd. the method for the 2nd record, wherein nitrogenous organic compound are to be selected from N, dinethylformamide and N-N-methyl-2-2-pyrrolidone N-at least a.
The 4th. the method for the 1st record, the method is characterized in that, in inert solvent, take off the IF reaction.
In preparation method of the present invention, formula (II) I-(CF
2)
nThe IF that takes off of the compound of-I (in the formula, n is 4～20 integer) expression reacts and can carry out in the presence of metallic zinc and organic compounds containing nitrogen.
Spendable organic compounds containing nitrogen has no particular limits, and can use any organic solvent (nitrogenous organic solvent) commonly used that is used for organic reaction and contains nitrogen-atoms.For example, amides (N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE, N, N-diisopropyl formamide etc.), amine (triethylamine etc.), pyridines (pyridine, picoline etc.), pyrrolidinone compounds (N-N-methyl-2-2-pyrrolidone N-(NMP) etc.), quinoline (quinoline, toluquinoline etc.) etc.In these compounds, preferred amide class and pyrrolidinone compounds, more preferably DMF and NMP.These nitrogenous compounds can use separately, or are used in combination more than 2 kinds or 2 kinds.
The consumption of nitrogenous organic compound has no particular limits, as long as can obtain the desired effect of the present invention, still for the compound of 1 mole of formula (II) expression, its consumption is generally about 0.01～about 100 moles, preferred about 0.5～about 10 moles.If the consumption of nitrogenous organic compound in above-mentioned scope, can obtain high conversion, this is favourable from economically.
As for metallic zinc, can use commercially available metallic zinc powder.The consumption of metallic zinc has no particular limits, as long as can obtain the desired effect of the present invention, still for the compound of 1 mole of formula (II) expression, its consumption is generally about 0.01～100 mole, preferred about 0.5～about 10 moles.If the consumption of metallic zinc in above-mentioned scope, can obtain high conversion, this is favourable from economically.
Temperature of reaction is-80 ℃ approximately～+ 200 ℃ approximately, preferred about 80～about 160 ℃.If range of reaction temperature is 80～160 ℃, speed of reaction is enough high, can obtain sufficient transformation efficiency, and this is an ideal from economically.
The compound of formula (II) expression and metallic zinc and nitrogenous organic solvent can any order mix; If but nitrogenous organic compound is added drop-wise in the mixed solution of the compound of formula (II) expression and metallic zinc, can obtain higher transformation efficiency.
Since the compound of formula (II) expression to take off the IF reaction be thermopositive reaction, therefore in order to control localized heat release, preferably before taking off IF reaction, with inert solvent (that is, do not participate in react solvent) compound of dilution formula (II) expression and/or nitrogenous organic compound.
The example of inert solvent has perfluor series solvent (specifically, carbonatoms is about chain of 5～about 15 or ring-type perfluoro alkane, perfluoroamine, perfluor ether) etc.The example of commercially available perfluoro solvent has the solvent (3M society system) of commodity FC-43 by name and FC-70.The consumption of inert solvent has no particular limits, the setting that can suit, but, use about 0.1g～about 20g, preferably about 1g～about 5g solvent usually for the compound that 1g formula (II) is represented.
Reaction times has no particular limits, and can set aptly according to the reaction conditions of temperature of reaction etc., is generally about 1 minute～about 5 hours, preferred about 10 minutes～about 1 hour.
Reaction pressure has no particular limits, but reaction (for example, is carried out under about 0.05～0.2Mpa) the condition at normal pressure or decompression usually.
So the perfluor alkadiene that obtains can separate with reaction mixture by the isolated or purified method of routine.
Therefore, the invention provides and do not use expensive and reluctant reagent, easily prepare the method for perfluor alkadiene.
The best approach that carries out an invention
Illustrate in greater detail the present invention by the following examples, but the invention is not restricted to these embodiment.
Embodiment 1
In the 100ml eggplant type flask that links to each other with the dry ice cold-trap, have ジ system ロ one ト (dimroth) condenser, add 15.0g I-CF
2CF
2CF
2CF
2-I and 4.1g (2 equivalent) zinc powder, then under agitation, with shell type well heater slow heated mixt, to internal temperature be 120 ℃.Mixture is incubated 30 minutes under this temperature.Next,, slowly add 4.9g (2 equivalent) dry DMF, continue reaction from dropping funnel for the control heat release.After about 30 minutes, reclaimed 4.4g gas in the cold-trap.The analytical results of gas composition: perfluorobutadiene (CF
2=CF-CF=CF
2) 65%, 1327pcy (CF
2H-CF
2-CF=CF
2) 23%, perfluorocyclobutane 7%, 338pcc (CF
2H-CF
2-CF
2-CF
2H) 2% (remaining 3% be other by products).Behind the ordinary method divided gas flow, obtain 2.9g target compound perfluorobutadiene.
Embodiment 2
In the 500ml eggplant type flask that links to each other with the dry ice cold-trap, have ジ system ロ one ト condenser, add 40.0g I-CF
2CF
2CF
2CF
2-I, 120g perfluoro solvent (FC-70,3M society system) and 23g (4 equivalent) zinc powder, then under agitation, with shell type well heater slow heated mixt, to internal temperature be 140 ℃.Mixture is incubated 30 minutes under this temperature.Next,, slowly add 25.7g (4 equivalent) dry DMF, continue reaction from dropping funnel for the control heat release.After about 30 minutes, reclaimed 10.4g gas in the cold-trap.The analytical results of gas composition: perfluorobutadiene (CF
2=CF-CF=CF
2) 88%, 1327pcy (CF
2H-CF
2-CF=CF
2) 7%, perfluorocyclobutane 1%, 338pcc (CF
2H-CF
2-CF
2-CF
2H) 1% (remaining 3% be other by products).Behind the ordinary method divided gas flow, obtain 9.2g target compound perfluorobutadiene.
Embodiment 3
In the 200ml eggplant type flask that links to each other with the dry ice cold-trap, have ジ system ロ one ト condenser, add 20.0g I-CF2CF2CF2CF2-I, 40.0g perfluoro solvent (FC-70,3M society system) and 5.7g (2 equivalent) zinc powder, then under agitation, with the slow heated mixt of shell type well heater, to internal temperature be 140 ℃.Mixture is incubated 30 minutes under this temperature.Next,, slowly add 8.7g (2 equivalent) NMP (N-N-methyl-2-2-pyrrolidone N-), continue reaction from dropping funnel for the control heat release.After about 30 minutes, reclaimed 4g gas in the cold-trap.The analytical results of gas composition: perfluorobutadiene (CF
2=CF-CF=CF
2) 85%, 1327pcy (CF
2H-CF
2-CF=CF
2) 10%, perfluorocyclobutane 3%, 338pcc (CF
2H-CF
2-CF
2-CF
2H) 2%.Behind the ordinary method divided gas flow, obtain 3.4g target compound perfluorobutadiene.
Embodiment 4
In the 200ml eggplant type flask that links to each other with the dry ice cold-trap, have ジ system ロ one ト condenser, add 20.0g I-CF
2CF
2CF
2CF
2-I, 40.0g perfluoro solvent (FC-70,3M society system) and 5.7g (2 equivalent) zinc powder, then under agitation, with shell type well heater slow heated mixt, to internal temperature be 140 ℃.Mixture is incubated 30 minutes under this temperature.Next,, slowly add 11.3g (2 equivalent) quinoline, continue reaction from dropping funnel for the control heat release.After about 30 minutes, reclaimed 2.5g gas in the cold-trap.The analytical results of gas composition: perfluorobutadiene (CF
2=CF-CF=CF
2) 85%, 1327pcy (CF
2H-CF
2-CF=CF
2) 6%, perfluorocyclobutane 6%, 338pcc (CF
2H-CF
2-CF
2-CF
2H) 3%.Behind the ordinary method divided gas flow, obtain 2.1g target compound perfluorobutadiene.
Embodiment 5
In the 1000ml eggplant type flask that links to each other with the dry ice cold-trap, have ジ system ロ one ト condenser, add 200g I-CF
2CF
2CF
2CF
2-I and 57g (2 equivalent) zinc powder, then under agitation, with shell type well heater slow heated mixt, to internal temperature be 120 ℃.Mixture is incubated 30 minutes under this temperature.Next,, slowly add 128g (4 equivalent) dry DMF, continue reaction from dropping funnel for the control heat release.After about 30 minutes, reclaimed 60.6g gas in the cold-trap.The analytical results of gas composition: perfluorobutadiene (CF
2=CF-CF=CF
2) 90%, 1327pcy (CF
2H-CF
2-CF=CF
2) 6%, perfluorocyclobutane 1%, 338pcc (CF
2H-CF
2-CF
2-CF
2H) 1% (remaining 2% be other by products).Behind the ordinary method divided gas flow, obtain 54.5g target compound perfluorobutadiene.
Embodiment 6
With the stainless steel reactor of 10L that reflux exchanger links to each other with the dry ice cold-trap in, add 5.0kg (11 moles) I-CF
2CF
2CF
2CF
2-I, 10kg perfluoro solvent (FC-43,3M society system) and 1.73kg (26 moles) zinc powder (Northeast chemistry system #48005-01, grade＞85%) under agitation are warming up to 120 ℃ then, and kept this temperature 30 minutes.Next, on one side the heat release of monitoring reaction, on one side with 2 hour time dropping 0.80kg (11 moles) DMF.Continue reaction again after 6 hours, analyze the liquid of collecting in the cold-trap.Obtain 1.5kg target compound perfluorobutadiene.
Claims (4)
1. the method for the perfluor alkadiene that takes off IF prepared in reaction formula (I) expression of the compound of a through type (II) expression,
CF
2＝CF-(CF
2)
n-4-CF＝CF
2 (I)
In the formula, n is 4～20 integer;
I-(CF
2)
n-I (II)
In the formula, the definition of n is the same,
The method is characterized in that, in the presence of metallic zinc and organic compounds containing nitrogen, take off the IF reaction.
2. the method for claim 1 record, wherein said nitrogenous organic compound is to be selected from N, dinethylformamide, N,N-dimethylacetamide, N, N-diisopropyl formamide, triethylamine, pyridine, picoline, N-N-methyl-2-2-pyrrolidone N-, quinoline and toluquinoline at least a.
3. the method for claim 2 record, wherein said nitrogenous organic compound is to be selected from N, dinethylformamide and N-N-methyl-2-2-pyrrolidone N-at least a.
4. the method for claim 1 record the method is characterized in that, takes off the IF reaction in inert solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3823/2000 | 2000-01-12 | ||
| JP2000003823A JP4573005B2 (en) | 2000-01-12 | 2000-01-12 | Method for producing perfluoroalkadiene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1423626A CN1423626A (en) | 2003-06-11 |
| CN1167655C true CN1167655C (en) | 2004-09-22 |
Family
ID=18532703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008182779A Expired - Fee Related CN1167655C (en) | 2000-01-12 | 2000-12-28 | Process for production of perfluoroalkadienes |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6610896B2 (en) |
| EP (1) | EP1247791B1 (en) |
| JP (1) | JP4573005B2 (en) |
| KR (1) | KR100614996B1 (en) |
| CN (1) | CN1167655C (en) |
| DE (1) | DE60026607T8 (en) |
| TW (1) | TWI237629B (en) |
| WO (1) | WO2001051436A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080300432A1 (en) * | 2004-08-26 | 2008-12-04 | Vicki Hedrick | Chemical Production Processes and Systems |
| ITMI20050818A1 (en) | 2005-05-05 | 2006-11-06 | Solvay Solexis Spa | DEALOGENATION PROCESS |
| ITMI20050817A1 (en) | 2005-05-05 | 2006-11-06 | Solvay Solexis Spa | DEALOGENATION PROCESS |
| KR100852900B1 (en) * | 2007-04-20 | 2008-08-19 | (주)후성 | Method of manufacturing perfluroalkadiene |
| JP5547089B2 (en) | 2008-01-08 | 2014-07-09 | ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア | Method for synthesizing perfluorobutadiene |
| EP3590912A4 (en) * | 2017-02-03 | 2020-12-30 | Daikin Industries, Ltd. | Method for producing perfluoroalkadiene compounds |
| JP6798468B2 (en) * | 2017-10-23 | 2020-12-09 | ダイキン工業株式会社 | Method for producing hexafluorobutadiene |
| JP7337759B2 (en) * | 2018-06-15 | 2023-09-04 | ダイキン工業株式会社 | Method for producing perfluoroalkadiene compound |
| JP7158906B2 (en) * | 2018-06-15 | 2022-10-24 | ダイキン工業株式会社 | Method for producing perfluoroalkadiene compound |
| JP6813003B2 (en) * | 2018-06-15 | 2021-01-13 | ダイキン工業株式会社 | Method for producing perfluoroalkaziene compound |
| EP3865468A4 (en) | 2018-10-09 | 2023-01-11 | Daikin Industries, Ltd. | Process for producing perfluoroalkyne compound |
| JP7168959B2 (en) * | 2019-01-24 | 2022-11-10 | 国立大学法人京都工芸繊維大学 | Method for producing α,ω-perfluoroalkadiene and metal complex |
| CN111072526B (en) * | 2019-12-26 | 2022-05-27 | 浙江巨化技术中心有限公司 | Preparation method of resin monomer for ion exchange membrane |
| JP7011197B2 (en) * | 2020-05-12 | 2022-01-26 | ダイキン工業株式会社 | Method for producing hexafluorobutadiene |
| JP2020203942A (en) * | 2020-09-16 | 2020-12-24 | ダイキン工業株式会社 | Production method of perfluoroalkadiene compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1207496B (en) * | 1985-05-29 | 1989-05-25 | Montefluos Spa | PROCEDURE FOR THE SYNTHESIS OF HEXAFLUOROBUTADIENE AND HIGHER FLUORINATED DIENES. |
| IT1199678B (en) * | 1986-11-27 | 1988-12-30 | Ausimont Spa | PROCEDURE FOR THE SYNTHESIS OF PERFLUOROALCADIENI |
| IT1224323B (en) * | 1988-06-30 | 1990-10-04 | Ausimont Spa | PROCEDURE FOR THE PREPARATION OF FLUORINATED CONJUGATED OIL PRODUCTS AND PRODUCTS OBTAINED |
-
2000
- 2000-01-12 JP JP2000003823A patent/JP4573005B2/en not_active Expired - Fee Related
- 2000-12-28 EP EP00987791A patent/EP1247791B1/en not_active Expired - Lifetime
- 2000-12-28 US US10/169,076 patent/US6610896B2/en not_active Expired - Lifetime
- 2000-12-28 DE DE60026607T patent/DE60026607T8/en active Active
- 2000-12-28 WO PCT/JP2000/009392 patent/WO2001051436A1/en active IP Right Grant
- 2000-12-28 CN CNB008182779A patent/CN1167655C/en not_active Expired - Fee Related
- 2000-12-28 KR KR1020027008885A patent/KR100614996B1/en not_active IP Right Cessation
-
2001
- 2001-01-12 TW TW090100878A patent/TWI237629B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP1247791A4 (en) | 2005-05-11 |
| CN1423626A (en) | 2003-06-11 |
| EP1247791A1 (en) | 2002-10-09 |
| US6610896B2 (en) | 2003-08-26 |
| DE60026607T8 (en) | 2007-08-02 |
| JP2001192345A (en) | 2001-07-17 |
| WO2001051436A1 (en) | 2001-07-19 |
| DE60026607T2 (en) | 2006-12-21 |
| US20020193643A1 (en) | 2002-12-19 |
| TWI237629B (en) | 2005-08-11 |
| JP4573005B2 (en) | 2010-11-04 |
| KR20020070473A (en) | 2002-09-09 |
| KR100614996B1 (en) | 2006-08-25 |
| DE60026607D1 (en) | 2006-05-04 |
| EP1247791B1 (en) | 2006-03-08 |
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